Elucidating Mechanism and Selectivity in Pyridine Functionalization through Silylium Catalysis.

The functionalization of aromatic N-heterocycles through silylium activation demonstrates exceptional selectivity and efficiency. Density functional theory (DFT) calculations unveil the detailed silylium catalysis mechanism and elucidate the origins of selectivity in this reaction. The phosphoramidimidate sulfonamide (PADI) precatalyst orchestrates of the catalytic cycle via three elementary steps. The Brønsted acidity of precatalyst significantly influences both the formation of silylium-based Lewis acid active species and the silylium activation of pyridine. Unlike disulfonimide (DSI)-type precatalysts, both Tf2NH and PADI precatalysts with strong acidities can easily promote the generation of activated silylium pyridine species. A semi-enclosed 'rigid' electronegative cavity in PADI-type anions constructs a well-defined recognition site, facilitating engagement with the positively charged silylium pyridine species. Due to the high electrophilicity and less steric demand at the C4-position of the pyridine substrate, the product with C4-regioselectivity was predominantly generated.

Theoretical comparison of fructose with methylglucoside for the production of formate and levulinate catalyzed by Brønsted acids in a methanol solution.

For the conversion of fructose/methylglucoside (MG) into both methyl formate (MF) and methyl levulinate (MLev), the C-source of formate [HCOO]- remains unclear at the molecular level. Herein, reaction mechanisms catalyzed by [CH3OH2]+ in a methanol solution were theoretically investigated at the PBE0/6-311++G(d,p) level. For the conversion of fructose into MF and MLev, the formate [HCOO]- comes from the C1-atom of fructose, in which the rate-determining step lies in the reaction of 5-hydroxymethylfurfural (HMF) with CH3OH to yield MF and MLev. The reaction of fructose with CH3OH kinetically tends to generate HMF intermediates rather than yield (MF + MLev). When MG is dissolved in a methanol solution, its O2, O3, and O4 atoms are closer to the first layer of the solvent than O1, O5, and O6 atoms. For the dehydration of MG with methanol into MF and MLev, the formate [HCOO]- stems from the dominant C1- and secondary C3-atoms of MG. Kinetically, MG is ready to yield (MF + MLev), whereas fructose can induce the reaction to remain at the HMF intermediate, inhibiting the further conversion of HMF with CH3OH into MF and MLev. If MG isomerizes into fructose, the reaction will be more preferable for yielding HMF rather than (MF + MLev).

Mechanism of CO2 in promoting the hydrogenation of levulinic acid to γ-valerolactone catalyzed by RuCl3 in aqueous solution.

A Ru-containing complex shows good catalytic performance toward the hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) with the assistance of organic base ligands (OBLs) and CO2. Herein, we report the competitive mechanisms for the hydrogenation of LA to GVL, 4-oxopentanal (OT), and 2-methyltetrahydro-2,5-furandiol (MFD) with HCOOH or H2 as the H source catalyzed by RuCl3 in aqueous solution at the M06/def2-TZVP, 6-311++G(d,p) theoretical level. Kinetically, the hydrodehydration of LA to GVL is predominant, with OT and MFD as side products. With HCOOH as the H source, initially, the OBL (triethylamine, pyridine, or triphenylphosphine) is responsible for capturing H+ from HCOOH, leading to HCOO- and [HL]+. Next, the Ru3+ site is in charge of sieving H- from HCOO-, yielding [RuH]2+ hydride and CO2. Alternatively, with H2 as the H source, the OBL stimulates the heterolysis of H-H bond with the aid of Ru3+ active species, producing [RuH]2+ and [HL]+. Toward the [RuH]2+ formation, H2 as the H source exhibits higher activity than HCOOH as the H source in the presence of an OBL. Thereafter, H- in [RuH]2+ gets transferred to the unsaturated C site of ketone carbonyl in LA. Afterwards, the Ru3+ active species is capable of cleaving the C-OH bond in 4-hydroxyvaleric acid, yielding [RuOH]2+ hydroxide and GVL. Subsequently, CO2 promotes Ru-OH bond cleavage in [RuOH]2+, forming HCO3- and regenerating the Ru3+-active species owing to its Lewis acidity. Lastly, between the resultant HCO3- and [HL]+, a neutralization reaction occurs, generating H2O, CO2, and OBLs. Thus, the present study provides insights into the promotive roles of additives such as CO2 and OBLs in Ru-catalyzed hydrogenation.

Selective Stereoretention of Carbohydrates upon C-C Cleavage Enabling D-Glyceric Acid Production with High Optical Purity over a Ag/γ-Al2O3 Catalyst.

Chiral carboxylic acid production from renewable biomass by chemocatalysis is vitally important for reducing our carbon footprint, but remains underdeveloped. We herein establish a strategy that make use of a stereogenic center of biomass to achieve a rare example of D-glyceric acid production with the highest yield (86.8 %) reported to date as well as an excellent ee value (>99 %). Unlike traditional asymmetric catalysis, chiral catalysts/additives are not required. Ample experiments combined with quantum chemical calculations established the origins of the stereogenic center and catalyst performance. The chirality at C4 in D-xylose was proved to be retained and successfully delivered to C2 in D-glyceric acid during C-C cleavage. The remarkable cooperative-roles of Ag+ and Ag0 in the constructed Ag/γ-Al2O3 catalyst are disclosed as the crucial contributors. Ag+ was responsible for low-temperature activation of D-xylose, while Ag0 facilitated the generation of active O* from O2. Ag+ and active O* cooperatively promoted the precise cleavage of the C2-C3 bond, and more importantly O* allowed the immediate fast oxidization of the D-glyceraldehyde intermediate to stabilize D-glyceric acid, thereby inhibiting the side reaction that induced racemization. This strategy makes a significant breakthrough in overcoming the limitation of poor enantioselectivity in current chemocatalytic conversion of biomass.

Theoretical Study on Cooperation Catalysis of Chiral Guanidine/ Copper(I) in Asymmetric Azide-Alkyne Cycloaddition/[2 + 2] Cascade Reaction.

Density functional theory (DFT) calculations with BP86-D3(BJ) functionals were employed to reveal the mechanism and stereoselectivity of chiral guanidine/copper(I) salt-catalyzed stereoselective three-component reaction among N-sulfonyl azide, terminal alkyne, and isatin-imine for spiroazetidinimines that was first reported by Feng and Liu (Angew. Chem. Int. Ed. 2018, 57, 16852-16856). For the noncatalytic cascade reaction, the denitrogenation to generate ketenimine species was the rate-determining step, with an activation barrier of 25.8-34.8 kcal mol-1. Chiral guanidine-amide promoted the deprotonation of phenylacetylene, generating guanidine-Cu(I) acetylide complexes as active species. In azide-alkyne cycloaddition, copper acetylene coordinated to the O atom of the amide moiety in guanidium, and TsN3 was activated by hydrogen bonding, affording the Cu(I)-ketenimine species with an energy barrier of 3.5∼9.4 kcal mol-1. The optically active spiroazetidinimine oxindole was constructed via a stepwise four-membered ring formation, followed by deprotonation of guanidium moieties for C-H bonding in a stereoselective way. The steric effect of the bulky CHPh2 group and chiral backbone in the guanidine, combined with the coordination between the Boc group in isatin-imine with a copper center, played important roles in controlling the stereoselectivity of the reaction. The major spiroazetidinimine oxindole product with an SS configuration was formed in a kinetically more favored way, which was consistent with the experimental observation.

Coordination of sorbitol to Ga(OTf)3 in the liquid phase: an experimental and theoretical study.

In a solution of sorbitol (SBT) and Ga(OTf)3 compounds, the coordination of sorbitol (SBT) to [Ga(OTf)n]3-n (n = 0-3) has been investigated, using both ESI-MS spectra and density functional theory (DFT) calculations at the M06/6-311++g(d,p), aug-cc-pvtz level using a polarized continuum model (PCM-SMD). In sorbitol solution, the most stable conformer of sorbitol includes three intramolecular H-bonds, i.e., O2H⋯O4, O4H⋯O6, and O5H⋯O3. Through ESI-MS spectra, in a tetrahydrofuran solution of both SBT and Ga(OTf)3 compounds, five main species are observed, i.e., [Ga(SBT)]3+, [Ga(OTf)]2+, [Ga(SBT)2]3+, [Ga(OTf)(SBT)]2+, and [Ga(OTf)(SBT)2]2+. Through DFT calculations, in a solution of sorbitol (SBT) and Ga(OTf)3 compounds, the Ga3+ cation tends to form five six-coordination complexes, i.e., [Ga(η2O,O-OTf)3], [Ga(η3O2-O4-SBT)2]3+, [(η2O,O-OTf)Ga(η4O2-O5-SBT)]2+, [(η1O-OTf)(η2O2,O4-SBT)Ga(η3O3-O5-SBT)]2+, and [(η1O-OTf)(η2O,O-OTf)Ga(η3O3-O5-SBT)]+, which are in good agreement with the experimental observation of the ESI-MS spectra. For both [Ga(OTf)n]3-n (n = 1-3) and [Ga(SBT)m]3+ (m = 1, 2) complexes, the negative charge transfer from ligands to the Ga3+-center plays an important role in their stability, because of the strong polarization of the Ga3+ cation. For [Ga(OTf)n(SBT)m]3-n (n = 1, 2; m = 1, 2) complexes, the negative charge transfer from ligands to the Ga3+-center plays an essential role in their stability, accompanied by an electrostatic interaction between the Ga3+-center and ligands and/or spatial inclusion of ligands toward the Ga3+-center.

Cooperative Catalysis Mechanism of Brønsted and Lewis Acids from Al(OTf)3 with Methanol for ß-Cellobiose-to-Fructose Conversion: An Experimental and Theoretical Study.

Al-containing catalysts, e.g., Al(OTf)3, show good catalytic performance toward the conversion of cellulose to fructose in methanol solution. Here, we report the catalytic isomerization and alcoholysis mechanisms for the conversion of cellobiose to fructose at the PBE0/6-311++G(d,p), aug-cc-pVTZ theoretical level, combining the relevant experimental verifications of electrospray ionization mass spectrometry (ESI-MS), high-performance liquid chromatography (HPLC), and the attenuated total reflection-infrared (ATR-IR) spectra. From the alcoholysis of Al(OTf)3 in methanol solution, the catalytically active species involves both the [CH3OH2]+ Brønsted acid and the [Al(CH3O)(OTf)(CH3OH)4]+ Lewis acid. There are two reaction pathways, i.e., one through glucose (glycosidic bond cleavage followed by isomerization, w-G) and another through cellobiulose (isomerization followed by glycosidic bond cleavage, w-L). The Lewis acid ([Al(CH3O)(OTf)(CH3OH)4]+) is responsible for the aldose-ketose tautomerization, while the Brønsted acid ([CH3OH2]+) is in charge of ring-opening, ring-closure, and glycosidic bond cleavage. For both w-G and w-L, the rate-determining steps are related to the intramolecular [1,2]-H shift between C1-C2 for the aldose-ketose tautomerization catalyzed by the [Al(CH3O)(OTf)(CH3OH)4]+ species. The Lewis acid ([Al(CH3O)(OTf)(CH3OH)4]+) exhibits higher catalytic activity toward the aldose-ketose tautomerization of glycosyl-chain-glucose to glycosyl-chain-fructose than that of chain-glucose to chain-fructose. Besides, the Brønsted acid ([CH3OH2]+) shows higher catalytic activity toward the glycosidic bond cleavage of cellobiulose than that of cellobiose. Kinetically, the w-L pathway is predominant, whereas the w-G pathway is minor. The theoretically proposed mechanism has been experimentally testified. These insights may advance on the novel design of the catalytic system toward the conversion of cellulose to fructose.

Enhancement of carbon nanotubes on microalgal-fungal consortium formation and wastewater treatment.

As a promising material with an efficient light capture capability, a low amount of carbon nanotubes can affect growth and photosynthesis by regulating microalgal cells, thereby enhancing the pollutant removal efficiency in wastewater. In this study, microalgal-fungal consortia of Chlorella vulgaris and Ganoderma lucidum were developed with different types and concentrations of carbon nanotubes. The treatment effect of microalgal-fungal consortia on simulated digestate was also studied. The results demonstrate that 1.5 mg/L of carboxylated multi-walled carbon nanotubes remarkably promoted the formation, growth and photosynthesis of consortium. The dry weight and chlorophyll a content reached 19.3 ± 0.53 mg/symbiont and 27.3 ± 0.52 µg/L, respectively. Moreover, the removal efficiency of chemical oxygen demand, total nitrogen, total phosphorus and tetracycline hydrochloride were 94.1%, 65.5%, 61.9% and 96.2%, respectively. Overall, these findings suggest a promising future for the use of carbon nanotubes in wastewater treatment by regulating microalgal-fungal consortia.

Removal of tetracycline from water by catalytic photodegradation combined with the microalga Scenedesmus obliquus and the responses of algal photosynthesis and transcription.

The antibiotic tetracycline (TC) and its degradation products (TDPs) in degradation solution present serious environmental problems, such as human health damage and ecological risk; thus further treatment is required before being released into the aquatic environment. Furthermore, their environmental impact on microalgae remains unclear. In this study, TC was degraded by photocatalysis using birnessite and UV irradiation, followed by biological purification using the microalga Scenedesmus obliquus. In addition, the photosynthetic activity and transcription of the microalgae were examined to evaluate the toxicity of TC and TDPs. The results show that photocatalytic degradation efficiency reached 92.7% after 30 min, and 11 intermediate products were detected. The microalgae achieved a high TC removal efficiency (99.7%) after 8 days. Exposure to the degraded TC solution (D) resulted in significantly lower (p < 0.05) biomass than the pure TC (T), and S. obliquus in the T treatment showed better resilience than the D treatment. Transcriptomic assays for different treatments revealed differential gene expression mainly involving the photosynthesis, ribosome, translation and peptide metabolic progresses. The up-regulation of photosynthesis-related genes and differential expression of chloroplast genes may be important for S. obliquus to acquire high photosynthetic efficiency and growth recovery when exposed to TC and TDPs. Our study provides a reference for TC removal using a combination of catalytic degradation and microalgal purification, and it is also helpful for understanding the environmental risk of TDPs in natural aquatic environments.

Mechanistic Study of Asymmetric Alkynylation of Isatin-Derived Ketimine Mediated by a Copper/Guanidine Catalyst.

In this work, we performed a mechanistic study of asymmetric alkynylation of isatin-derived N-Boc ketimine that was first reported by Feng, Liu, and co-workers (Chem. Commun. 2018, 54, 678-681). Guanidine-amide promoted the formation of highly nucleophilic copper acetylene species by abstracting the terminal proton of phenylacetylene with an imine moiety. The guanidinium salt-Cu(I) complex was the most active species in the addition of the C═N bond, in which copper acetylene coordinated to the O atom of the amide moiety, and the isatin-derived ketimine substrate was activated by hydrogen bonding as well as tert-butoxycarbonyl···Cu(I) coordination. Due to weak interaction between Cu(I) and the Ph group in the amide of guanidine, as well as the repulsion between the tert-butyl group in ketimine and the cyclohexyl group in guanidine, the copper acetylene preferred to attack isatin-derived ketimine from the re-face, leading to the S-configuration product with excellent stereoselectivity. The affinity of the counterion for the Cu(I) center in the copper salt affected the deprotonation of phenylacetylene and the formation of guanidinium salt active species. In contrast to CuBr and CuCl, the combination of CuI with aniline-derived guanidine-amide exhibited high catalytic activity and a chiral induction effect, contributing to a high turnover frequency (9.70 × 10-4 s-1) in catalysis and ee%.

Effects of Tetracycline on Scenedesmus obliquus Microalgae Photosynthetic Processes.

Tetracycline (TC) antibiotics can be detected worldwide in the aquatic environment due to their extensive use and low utilization efficiency, and they may affect the physiological processes of non-target organisms. In this study, the acute and sub-acute toxicities of TC on the freshwater microalga Scenedesmus obliquus were investigated with an emphasis on algal photosynthesis and transcription alterations during an 8 d TC exposure. The results showed that the IC10, IC30 and IC50 values were 1.8, 4.1 and 6.9 mg/L, respectively. During sub-acute exposure, the microalgae of the IC10 treatment was able to recover comparable growth to that of the control by day 7, while significantly lower cell densities were observed in the IC30 and IC50 treatments at the end of the exposure. The photosynthetic efficiency Fv/FM of S. obliquus first decreased as the TC concentration increased and then returned to a level close to that of the control on day 8, accompanied by an increase in photosynthetic activities, including light harvesting, electron transport and energy dissipation. Transcriptomic analysis of the IC10 treatment (1.8 mg/L TC) revealed that 2157 differentially expressed genes were up-regulated and 1629 were down-regulated compared with the control. KEGG and GO enrichments demonstrated that 28 photosynthesis-related genes involving light-harvesting chlorophyll protein complex, photosystem I, photosystem II, photosynthetic electron transport and enzymes were up-regulated, which may be the factor responsible for the enhanced photosynthesis and recovery of the microalgae. Our work may be helpful not only for gaining a better understanding of the environmental risk of TC at concentrations close to the real levels in natural waters, but also for explaining photosynthesis and related gene transcription induced by antibiotics.

Metagenomics unraveled the characteristics and microbial response to hypersaline stress in salt-tolerant aerobic granular sludge.

In this study, the salt-tolerant aerobic granular sludge (SAGS) was cultivated with the increased salinity (0-9% NaCl), showing oval shape, and clear outline. The related sludge characteristics in the formation process of SAGS as well as the effects of salinity on the performance (removal ability, sludge biomass and EPS component) of SAGS were evaluated. Increased salinity accelerated the formation of SAGS, and resulted in the excess secretion of EPS. Relationship between EPS and settling capacity of SAGS was determined, with the increase of salinity, SVI decreased linearly and the sedimentation performance of granular sludge was enhanced. Pearson correlation analysis showed that shorter settling time (3 min) and longer anaerobic influent time (30 min) were beneficial to the operation of SAGS reactor. Metagenomics results showed that the SAGS was dominated by Candida, Halomonas and other salt-tolerant bacteria, the enrichment of these salt-tolerant microbes played an important role in maintaining the stability of granular sludge system and improving the overall salt-tolerant performance. Compared with S9 samples, the proteome regulation in S0 sample was more active and the abundance of Cell motility related proteins was 5 times higher than that in S9 samples. Extracellular structure related proteins was more active in S9, and its abundance was 3.6 times that of S0.

Metabolomics revealed the photosynthetic performance and metabolomic characteristics of Euglena gracilis under autotrophic and mixotrophic conditions.

Photosynthetic and metabolomic performance of Euglena gracilis was examined and compared under autotrophic and mixotrophic conditions. Autotrophic protozoa (AP) obtained greater biomass (about 33% higher) than the mixotrophic protozoa (MP) after 12 days of growth. AP maintained steady photosynthesis, while MP showed a remarkable decrease in photosynthetic efficiency and dropped to an extremely low level at day 12. In MP, low light absorption and photosynthetic electron transport efficiency, and high energy dissipation were reflected by the chlorophyll (chl a) fluorescence (OJIP) of the protozoa. The values of ΨO, ΦEo, and ETO/RC of MP decreased to extremely low levels, to 1/15, 1/46, and 1/9 those of AP, respectively, while DIO/RC increased to approximately 16 times that of AP. A total of 137 metabolites were showed significant differences between AP and MP. AP accumulated more monosaccharide, lipids, and alkaloids, while MP produced more amino acids, peptides, and long-chain fatty acids including poly-unsaturated fatty acids. The top nine most important enriched pathways obtained from KEGG mapping were related to ABC transporters, biosynthesis of amino acids, purine metabolism, and carbohydrate metabolism. There were significant differences between AP and MP in photosynthetic activity, metabolites, and metabolic pathways. This work presented useful information for the production of high value bioproducts in E. gracilis cultured under different nutritional conditions.

Dibenzo[b,f][1,4,5]chalcogenadiazepine Photoswitches: Conversion of Excitation Energy into Ring Strain.

Tetra-ortho-substituted, heteroaryl and cyclic azobenzenes have emerged as three key strategies on morphology design of photoswitch to diversify controllability. Cyclic azobenzene is of particular utilization in photo-energy conversion due to rigid and ring-strain structure. Despite the well-recognized diazocine, the photo-switching properties of seven-membered cyclic azobenzenes (diazepines) have yet been exploited. Herein, we report a family of dibenzo[b,f][1,4,5]chalcogenadiazepines (DBChDs) and their T-type photo-switching nature with tunable relaxation rate. Based on experiments together with DFT calculations, we found that an unsymmetric 2-bithiophenyl-dibenzo[b,f][1,4,5]thiadiazepine exhibited an efficient response to 445 nm laser stimulation (quantum efficiency, ΦZ→E =0.71) with millisecond relaxation half-life (t1/2 =40 ms). Photo-energy transduction efficiency was also exceptionally high with 29.1 % converted into ring-strain energy mainly loaded on azo π-bond.

Mechanism and Selectivity of Cyclopropanation of 3-Alkenyl-oxindoles with Sulfoxonium Ylides Catalyzed by a Chiral N,N'-Dioxide-Mg(II) Complex.

The mechanism and stereoselectivity of an asymmetric cyclopropanation reaction between 3-alkenyl-oxindole and sulfoxonium ylide catalyzed by a chiral N,N'-dioxide-Mg(II) complex were explored using the B3LYP-D3(BJ) functional and the def2-TZVP basis set. The noncatalytic reaction occurred via a stepwise mechanism, with activation barriers of 21.6-23.5 kcal mol-1. The C2-Cα bond formed followed by the carbanion SN2 substitution, constructing a three-membered ring in spiro-cyclopropyl oxindoles, accompanied by the release of dimethylsulfoxide. The electron-withdrawing N-protecting t-butyloxy carbonyl (Boc) and acetyl (Ac) groups in isatin enhanced the local electrophilicity of the C2 atom and the repulsion between the two COPh groups in the reactants, contributing to high reactivity as well as good diastereoselectivity results. The N-Boc-3-phenacylideneoxindole coordinated to the chiral ligand (L-PiPr2) in a bidentate fashion, forming a hexacoordinate-Mg(II) complex as the reactive species. The origin of enantioselectivity was from the shielding effect of 2,6-diisopropylphenyl groups in the ligand toward the si-face of oxindole. The repulsion between the SO(CH3)2 and COPh groups in 3-alkenyl-oxindole and the neighboring ortho-iPr group in the ligand directed the re-face of ylide to attack the re-face of oxindole preferably, contributing to the high diastereoselectivity of the product. A metal-ion-ligand matching relationship was important for a good asymmetric induction effect of the chiral N,N'-dioxide-metal catalyst. A large chiral cavity in the Zn(II) catalyst weakened the shielding effect of 2,6-diisopropylphenyl groups in the ligand toward the prochiral face of oxindole, leading to inferior enantioselectivity observed in the experiment.

Removal of atrazine in catalytic degradation solutions by microalgae Chlorella sp. and evaluation of toxicity of degradation products via algal growth and photosynthetic activity.

Degradation solutions containing atrazine need to be further purified before they are discharged into the aquatic environment. With the objectives of evaluating removal capacity of the microalga Chlorella sp. toward atrazine in degradation solutions and toxicity of the degradation products, we investigated the removal efficiency (RE) and bioaccumulation of atrazine in the microalgae after an 8 d exposure to diluted degraded solutions containing 40 µg/L and 80 µg/L of atrazine as well as degradation products in the present study. Moreover, pure atrazine solutions with similar concentrations were simultaneously inoculated with the microalgae in order to distinguish the influence of the products. The photocatalytic degradation results showed that 31.4% of atrazine was degraded after 60 min, and three degradation products, desisopropyl-atrazine (DIA), desethyl-atrazine (DEA), and desethyl-desisopropyl-atrazine (DEIA) were detected. After an 8-d exposure, 83.0% and 64.3% of atrazine were removed from the degraded solutions containing 40 µg/L and 80 µg/L of atrazine, respectively. In comparison with the control, i.e., pure atrazine solution with equal concentration, Chlorella sp. in the degraded atrazine solution showed lower RE and growth rate. The photosynthetic parameters, especially performance index (PIABS), clearly displayed the differences between treatments. The values of PIABS of Chlorella sp. cultured in degradation atrazine for 8 days were significantly lower (P < 0.01) than that in the corresponding pure atrazine, suggesting potential inhibitory effect of degradation products on the microalgae. Atrazine and the degradation products inhibited algal photosynthesis via depressed light absorption and electron transport, and reduced utilization of light energy via energy dissipation. Our results demonstrated that microalgae Chlorella sp. had an encouraging atrazine removal potential and the degradation products of atrazine may inhibit algal growth and removal capability. This study may be useful for the application of microalgae in herbicide wastewater treatment and understanding algal removal of atrazine in natural aquatic environment.

Guanidine-Amide-Catalyzed Aza-Henry Reaction of Isatin-Derived Ketimines: Origin of Selectivity and New Catalyst Design.

Density functional theory (DFT) calculations were performed to investigate the mechanism and the enantioselectivity of the aza-Henry reaction of isatin-derived ketimine catalyzed by chiral guanidine-amide catalysts at the M06-2X-D3/6-311+G(d,p)//M06-2X-D3/6-31G(d,p) (toluene, SMD) theoretical level. The catalytic reaction occurred via a three-step mechanism: (i) the deprotonation of nitromethane by a chiral guanidine-amide catalyst; (ii) formation of C-C bonds; (iii) H-transfer from guanidine to ketimine, accompanied with the regeneration of the catalyst. A dual activation model was proposed, in which the protonated guanidine activated the nitronate, and the amide moiety simultaneously interacted with the ketimine substrate by intermolecular hydrogen bonding. The repulsion of CPh3 group in guanidine as well as N-Boc group in ketimine raised the Pauli repulsion energy (∆EPauli) and the strain energy (∆Estrain) of reacting species in the unfavorable si-face pathway, contributing to a high level of stereoselectivity. A new catalyst with cyclopropenimine and 1,2-diphenylethylcarbamoyl as well as sulfonamide substituent was designed. The strong basicity of cyclopropenimine moiety accelerated the activation of CH3NO2 by decreasing the energy barrier in the deprotonation step. The repulsion between the N-Boc group in ketimine and cyclohexyl group as well as chiral backbone in the new catalyst raised the energy barrier in C-C bond formation along the si-face attack pathway, leading to the formation of R-configuration product. A possible synthetic route for the new catalyst is also suggested.

Mechanistic study of cellobiose conversion to 5-hydroxymethylfurfural catalyzed by a Brønsted acid with counteranions in an aqueous solution.

The fundamental understanding of the cooperativity of a Brønsted acid together with its anion for cellulose conversion in an aqueous solution is limited at present, in which cellobiose has usually been regarded as a bridge that connects monosaccharides and cellulose. The mechanism of ß-cellobiose conversion to 5-hydroxymethylfurfural (HMF) catalyzed by a Brønsted acid (H3O+) accompanied by counteranions in an aqueous solution has been studied using quantum chemical calculations at the M06-2X/6-311++G(d,p) level under a polarized continuum model (PCM-SMD). For the formation of the first HMF from cellobiose, there are three reaction pathways, i.e., through cellobiulose and glycosyl-HMF (C/H), through cellobiulose and fructose (C/F/H), and through glucose (C/G/H). For these three reaction pathways, the rate-determining steps are associated with the intramolecular [1,2]-H shift in the aldose-ketose tautomerization. C/H is the thermodynamically predominant pathway, while C/G/H is the kinetically dominant pathway. From cellobiose, the origin of the first HMF results kinetically from a small proportion of both C/H and C/F/H and from a large proportion of C/G/H. For the role of the counteranion in the catalytic activity of H3O+, the halide anions (Cl- and Br-) act as promoters, whereas both NO3- anions and carboxylate-containing anions behave as inhibitors. The roles of these anions in ß-cellobiose conversion to HMF can be correlated with their electrostatic potential and atomic number, which may cause a decrease in the relative enthalpy energy and the value of entropy on interacting with the cation moiety. These insights may advance the novel design of sustainable conversion systems for cellulose conversion into HMF.

Biorenewable hydrogen production through biomass gasification: A review and future prospects.

Hydrogen is recognized as one of the cleanest energy carriers, which can be produced from renewable biomass as a promising feedstock to achieve sustainable bioeconomy. Thermochemical technologies (e.g., gasification and pyrolysis) are the main routes for hydrogen production from biomass. Although biomass gasification, including steam gasification and supercritical water gasification, shows a high potential in field-scale applications, the selectivity and efficiency of hydrogen production need improvement to secure cost-effective industrial applications with high atom economy. This article reviews the two main-stream biomass-to-hydrogen technologies and discusses the significance of operating conditions and considerations in the catalytic system design. Challenges and prospects of hydrogen production via biomass gasification are explored to advise on the critical information gaps that require future investigations.

Cooperative Catalysis of Chiral Guanidine and Rh2(OAc)4 in Asymmetric O-H Insertion of Carboxylic Acid: A Theoretical Investigation.

We reported a mechanistic study on asymmetric O-H insertion reaction of α-diazoester with carboxylic acid using Rh2(OAc)4/chiral guanidine-amide as the cocatalyst by density functional theory [B3LYP-D3(BJ)/def2-TZVP//B3LYP-D3(BJ)/[6-31G**, SDD] (SMD, Et2O)]. The catalytic reaction included two stages: (i) formation of Rh-carbene species, subsequently by the construction of C-O bond forming enol and (ii) chiral guanidinium salt-assisted H-transfer to the enol. In cooperative catalysis, Rh2(OAc)4 helped to form an enol intermediate via high-reactivity Rh-carbene species, while the in situ-formed guanidium carboxylate acted as a chiral proton shuttle to construct a hydrogen bonding net for the stereo-determinant protonation. The repulsions between the phenyl group of the enol intermediate and the cyclohexyl as well as the ortho-substituted isopropyl group of chiral guanidine played important roles in controlling stereoselectivity. A disadvantageous steric arrangement in si-face attack weakened the stabilizing electrostatic and orbital interaction of reacting species in the H-transfer step, enhancing the pathway to form a predominant product with R-configuration in the two competing pathways. A model was proposed to explain the asymmetric induction of chiral guanidine-amide in protonation.